EP0232519B1 - Copolymer, process for its preparation and its use - Google Patents

Abstract

A textile auxiliary for improving the fastness of materials dyed or printed with a dyestuff is a copolymer of a diallylammonium monomer, a vinyl amide monomer and a (meth)acrylic ester monomer.

Description

The invention relates to a water-soluble crosslinked copolymer, a process for its preparation and its use as textile auxiliaries. The textile auxiliary is used in particular to improve the fastness properties of dyeings and prints with reactive dyes on cellulose material.

The textile material to be dyed or printed with reactive dyes can be used as e.g. Woven, knitted or also as yarn or thread and consist of cellulose or contain cellulose in addition to synthetic fibers. The dyeing of these materials can be carried out by known processes in that the textile material is treated in the manner of an exhaust process with a dye liquor containing reactive dye, usually at elevated temperature and in most commercial reactive dye types in the presence of alkali, or two-step processes such as e.g. the so-called pad-steam process or the cold retention process can be used. In the pad-steam process as well as in the cold residence process, the textile material is first padded with a reactive dye liquor, with alkali being present or being able to be applied in a separate impregnation step. In the pad-steam process, the dye fixation is then carried out by a steaming process, in the cold residence process by docking the impregnated goods and storing for several hours at normal temperature. Other fixing steps, such as The treatment of the goods which have been padded with an alkali-free reactive dye liquor with hot water glass solution has become known and is practiced industrially.

In all reactive dyeing and printing processes, a covalent chemical bond is created between the dye molecule and the cellulose molecule when the dyeing and printing process is sold. This type of dye is thus chemically anchored on the cellulose fiber.

Theoretically, dyeings and prints of reactive dyes on cellulose should have very high wet fastness properties. In practice, however, it turns out that this is not the case. The reasons for this are of different types and may not yet be known in their entirety. However, it can be said that a more or less large proportion of the reactive dye used for dyeing does not react with the cellulose fiber, but with water molecules. When reacting with water, the reactive dye loses its chemical binding ability to the cellulose and is only bound to the cellulose fiber molecule by secondary valence forces.

This phenomenon in the practical execution of the dyeings leads to the fact that dyeings and prints of reactive dyes on cellulose fibers only have high wet fastness properties if they are subjected to thorough washing after the dyeing operation. This required aftertreatment can require a technical effort that is close to the actual dyeing process. In particular, large amounts of water are required for the post-wash, and it is often necessary not only to show one, but to connect several washes in succession in order to achieve the desired high wet fastness of the dyeings.

There has also been no shortage of attempts and combinations to facilitate the washing out of the dye residues or to increase the wet fastness of dyeings and prints without having to increase the washing out effort.

DOS 29 10 583 discloses a soaping aid for dyeing and printing on textile materials, which is based on the use of an alkali aluminum silicate, optionally in combination with polyvinylpyrrolidone.

The problem of removing the portions of the hydrolyzed reactive dye, which are inherently water-soluble due to their substantivity to the cellulose fiber by secondary valence forces, and thus improving the wet fastness of the goods, has already been addressed in DOS 27 47 358 and DOS 28 43 645 been. According to the recommendation of DOS 27 47 358, polyamines, polyamides or polyurethanes and polyureas should be used for this purpose. According to DOS 28 43 645, alkoxylated polyamines such as e.g. alkoxylated polyethyleneimine can be used.

To solve another problem, namely the improvement in the wet fastness of noun dyeings, DAS 1 111 144 and 1 131 649, Belgian patent specification 625 711 and US patent specification 3,334,138 are used to aftertreatment the colorations with basic polyguanidine compounds and polymeric quaternized nitrogen-containing compounds Connections known.

It is also known for post-treatment with condensation products of cyanamide, formaldehyde and salts of organic amines or ammonium salts to improve the wet fastness of substantive dyeings.

Japanese patent 60.021987 describes reaction products of tertiary polyamines with polybasic carboxylic acids, such as, for example, to improve the wet fastness properties of reactively dyed or printed textiles. Phenolsulfonic acids, phenol carboxylic acids, polycarboxylic acids and their anhydrides. Due to their salt character, such products have the disadvantage that their action becomes weaker at high electrolyte concentrations. EP 100 300 describes the aftertreatment of textiles dyed with reactive dyes by condensation products from aminoalkanephosphonic acids with epichlorohydrin in the presence of stabilizers.

Polymers of polyalkylene polyamine with epichlorohydrin are also described in DE-OS 3 216 745 for improving the authenticity of dyeings.

However, all polymeric products based on peralkylated polyamines which have become known for the aftertreatment of reactive or substantive dyeings have the decisive disadvantage that unforeseen shifts in nuances can occur when dyeing with metal complex reactive dyes. In addition, their effectiveness is in some cases relatively low, so that large amounts are used The effects achieved are inadequate, particularly with regard to fastness to washing and also in wet rubbing fastnesses. Aftertreatment of reactive dyeings with the known condensation products of cyanamide, formaldehyde and amines, the fastness to perspiration which can be achieved still leaves much to be desired In addition, traces of formaldehyde are often found on the treated goods, and the aftertreatment with the basic compounds known from the prior art is also difficult in terms of process, since it must be very so be carried out carefully so that the reprecipitation of detached dye and the sticking of adsorbed dye components on the fiber surface is avoided. If the known aftertreatment agents are handled carelessly, the opposite of the desired effect can easily occur.

Another shortcoming of previously known aftertreatment agents based on peralkylated polyamines is that they split off in a pH range above 9 amines, such as methylamine or dimethylamine. When used in the trace area, this leads to considerable odor nuisance. Polyethyleneimine behaves similarly.

In principle, it is of course possible to produce reactive dyeings with high wet fastness simply by adding a sufficient number of the dyed material, e.g. Washes 6 to 8 consecutive washes several times with vigorous mechanical movement at high temperature and using effective detergents. However, this method is not only very time-consuming and requires a lot of equipment, but it also consumes a large amount of water, which is no longer sustainable in the sense of sensible use of the water, especially the drinking water supply. In addition, there are very high amounts of used washing liquors, which have to be worked up before being discharged into the sewage system or rivers.

Surprisingly, it has now been found that it is possible to save a large part of the otherwise necessary washing stages in the production of reactive dyeings and nevertheless achieve dyeings of outstanding fastness if the dyeings are subjected to an aftertreatment with a copolymer according to the invention.

• a) eine Diallylammonium-Komponente A der Formel I
  
  und
• b) einer Amid-Komponente B, die aus einer basischen Komponente B' der Formel 11
  
  und/gegebenenfalls einer Amid-Komponente B² der formel 111
  
  und/oder einer N-Vinylacylamid-Komponente B³ der Formel IV
  
  und/oder einer Ammonium-Komponente B⁴ der Formel V
  
  besteht und
• c) einer (Meth)Acrylester-Komponente C der Formel VI
  
  im Molverhältnis A:B:C = 1:(0,002 bis 4,5):(0 bis 0,5) und anschließender Vernetzung mit
• d) einer polyfunktionellen Alkylierungskomponente D und
• e) einer Polyamin-Komponente E, die aus einer Polyamin-Komponente E¹ der Formel VII
  
  und/oder einer Polyamin-Komponente E² der Formel VIII
  
  besteht, im Molverhältnis B¹:D:E = 1:(0,002 bis 2):(0 bis 5), wobei bedeuten:
  • R¹, R², R⁵, R⁶, R²¹ = (C₁―C₁₀)Alkyl,
  • R³, R⁴ R⁷, R⁸ , R¹¹, R¹², R¹⁸,R¹⁹, R²⁰ = Wasserstoff oder Methyl,
  • R⁹, R¹⁰, R¹³ = Wasserstoff oder (C₁―C₈)Alkyl,
  • R¹⁴ , R¹⁵, R¹⁶ , R¹⁷ = (C₁―C₈)Alkyl oder
  • R¹³ und R¹⁴ zusammen = -(CH₂)₃-, -(CH₂)₄- oder ―(CH₂)₅―,
  • R²² = ein Alkylenrest mit 1 bis 8 C-Atomen oder Phenylen,
  • R²³ Wasserstoff oder den Rest ―CO―R²²―COOH
  • X = -NH- oder -0-,
  • Y⊖, Z⊖ = ein einwertiges Anion oder ein einem einwertigen Anion äquivalenter Teil eines mehrwertigen Anions,
  • T = ⁅(CH₂)₅―NH⁆_vH
  • m, q = eine der Zahlen 2, 3, 4, 5, 6, 7, 8, 9 10,
  • n, p, r, w = eine der Zahlen 0, 1, 2 oder 3,
  • s, u = eine der Zahlen 2, 3, 4 oder 5,
  • v = die Zahl 0 oder eine so große Zahl, daß die Polyamin-Komponente E¹ unter Berücksichtigung von t ein Molgewicht von 1000 bis 30000 besitzt,
  • t = eine so große Zahl, daß unter Berücksichtigung von v das Molgewicht der Polyamin-Komponente E' der Formel VII zwischen 1000 und 30000 liegt.

The water-soluble copolymer according to the invention can be prepared by copolymerization

• a) a diallylammonium component A of formula I.
  
  and
• b) an amide component B, which consists of a basic component B 'of the formula 11
  
  and / optionally an amide component B ^{2 of} the formula 111
  
  and / or an N-vinylacylamide component B ^{3 of} the formula IV
  
  and / or an ammonium component B ^{4 of} the formula V
  
  exists and
• c) a (meth) acrylic ester component C of the formula VI
  
  in the molar ratio A: B: C = 1: (0.002 to 4.5) :( 0 to 0.5) and subsequent crosslinking with
• d) a polyfunctional alkylation component D and
• e) a polyamine component E, which consists of a polyamine component E ¹ of formula VII
  
  and / or a polyamine component E ^{2 of} the formula VIII
  
  exists, in the molar ratio B ¹ : D: E = 1: (0.002 to 2) :( 0 to 5), where:
  • R ¹ , R ² , R ⁵ , R ⁶ , R ²¹ = (C ₁ ―C ₁₀ ) alkyl,
  • R ³ , R ⁴ R ⁷ , R ⁸ , R ¹¹ , R ¹² , R ¹⁸ , R ¹⁹ , R ²⁰ = hydrogen or methyl,
  • R ⁹ , R ¹⁰ , R ¹³ = hydrogen or (C ₁ ―C ₈ ) alkyl,
  • R ¹⁴ , R ¹⁵ , R ¹⁶ , R ¹⁷ = (C ₁ ―C ₈ ) alkyl or
  • R ¹³ and R ¹⁴ together = - (CH ₂ ) ₃ -, - (CH ₂ ) ₄ - or - (CH ₂ ) ₅ -,
  • R ²² = an alkylene radical with 1 to 8 carbon atoms or phenylene,
  • R ^{23 is} hydrogen or the radical ―CO ― R ²² ―COOH
  • X = -NH- or -0-,
  • Y⊖, Z⊖ = a monovalent anion or a part of a polyvalent anion equivalent to a monovalent anion,
  • T = ⁅ (CH ₂ ) ₅ ―NH⁆ _v H
  • m, q = one of the numbers 2, 3, 4, 5, 6, 7, 8, 9 10,
  • n, p, r, w = one of the numbers 0, 1, 2 or 3,
  • s, u = one of the numbers 2, 3, 4 or 5,
  • v = the number 0 or a number so large that the polyamine component E ^{1 has} a molecular weight of 1,000 to 30,000 taking into account t,
  • t = a number so large that, taking into account v, the molecular weight of the polyamine component E 'of the formula VII is between 1000 and 30000.

The alkyl radicals R ¹ , R ² , R ⁵ , R ⁶ , R ⁹ , R ¹⁰ and R ¹³ to R ¹⁷ can be straight-chain or branched alkyl radicals.

In the diallylammonium component A of the formula I, the radicals R ¹ and R ² can be the same or different. R 'and R ^{2 are} preferably (C ₂ ―C ₄ ) alkyl and very preferably methyl. The radicals R ³ and R ⁴ can also be the same or different. They are preferably the same, and particularly preferably R ³ = R ⁴ = hydrogen.

X is preferably ―NH―.

The radicals Y⊖ and Z⊖ stand for monovalent anions, such as for nitrate, hydrogen sulfate, benzenesulfonate, acetate, trifluoroacetate, or for the part of a polyvalent anion equivalent to a monovalent anion, e.g. half a equivalent of sulfate, or a third equivalent of phosphate. The radicals Y⊖ and Z⊖ each represent a halogen anion, such as fluoride, bromide or iodide, preferably chloride.

The diallylammonium component A can consist of one compound of the formula I or of several compounds of the formula I. The other components B, B ¹ , B ² , B ³ , B ⁴ , C, D, E ¹ and E ² can each consist of one compound or of several compounds.

The amide component B consists of an amide component B ¹ and optionally an amide component B ² and / or an ― N ― vinylacylamide component B ³ and / or an ammonium component B ⁴ . The amide component B can consist, for example, of two individual components (for example B ¹ + B ² , B ¹ + B ³ ) or, for example, of three individual components (for example B ¹ + B ² + B ³ or B ¹ + B ³ + B ⁴ ) . The amide component B can also contain all four individual components (B ¹ + B ² + B ³ + B ⁴ ). In all the cases mentioned, the individual components B ¹ , B ² , B ³ , B ^{4 can in} turn consist of one or more individual compounds of the formulas given.

wobei in den Formeln Ila bis Ild R⁵, R⁶ und m insbesondere die bevorzugten Bedeutungen besitzen.In the formula II for the basic component B ^1, X is preferably ―NH― and n is preferably the number 0 and m is preferably one of the numbers 2, 3 or 4. R ⁵ and R ⁶ can be identical or different and are preferably (C ₁ ―C ₄ ) alkyl. R ⁷ and R ⁸ can also be the same or different. Examples of preferred compounds of the formula II are:

where in the formulas Ila to Ild R ⁵ , R ⁶ and m in particular have the preferred meanings.

wobei in den Formeln llla bis Illd R⁹ und R¹⁰ insbesondere die bevorzugten Bedeutungen besitzen.In formula III for the amide component B ² , p is preferably the number O. R ⁹ and R ¹⁰ on the one hand and R ¹¹ and R ¹² on the other hand can be the same or different. R ⁹ and R ^{10 are} preferably hydrogen or (C ₁ ―C ₄ ,) alkyl. Examples of preferred compounds of the formula III are:

where in the formulas IIla to Illd R ⁹ and R ¹⁰ in particular have the preferred meanings.

In formula IV for the N-vinylacylamide component B ³ , R ¹⁴ preferably denotes (C ₁ ―C ₄ ) alkyl. R ¹³ is preferably hydrogen or (C ₁ -C ₄ ) alkyl. R ¹³ and R ¹⁴ together preferably also mean - (CH ₂ ) ₃ -, - (CH ₂ ) ₄ - or - (CH ₂ ) ₅ -. Examples of preferred compounds of the formula IV are N-vinyl-2-pyrrolidone, N-vinyl-2-piperidinone, N-vinyl-e-caprolactam.

In the formula V for the ammonium component B ⁴ , X is preferably ―NH―. R ¹⁵ , R ¹⁶ and R ¹⁷ can be the same or different and are preferably (C ₁ ―C ₄ ) alkyl, very particularly preferably methyl, r is preferably the number O and q is preferably one of the numbers 2, 3 or 4.

In formula VI for the (meth) acrylic ester component C, R ²¹ generally means (C ₁ ―C ₈ ) A) ky), preferably (C ₁ ―C ₄ ) alkyl. When R ²⁰ = hydrogen, the compounds of the formulas VI are acrylic esters, and when R ²⁰ = methyl, methacrylic esters.

worin x die Zahl O, 1, 2 oder 3, vorzugsweise 0, ist und A, A' und A² gleiche oder verschiedene Reste der Formel ―CH₂A³ oder einen Epoxidrest (Oxiranrest) der Formeln X oder XI

bedeuten. A³ ist ein als Anion abspaltbarer Substituent, insbesondere Chlor, Brom oder lod, oder eine als Anion abspaltbare Gruppe, wie z.B. Hydroxyl, ein Sulfatorest, eine Phospatorest und Z steht für eine direkte Bindung oder für einen (x+2)-valenten organischen Rest.The polyfunctional alkylation component D has, for example, the formula IX

wherein x is the number O, 1, 2 or 3, preferably 0, and A, A 'and A ^{2 are} identical or different radicals of the formula ―CH ₂ A ³ or an epoxy radical (oxirane radical) of the formulas X or XI

mean. A ³ is a substituent which can be split off as an anion, in particular chlorine, bromine or iodine, or a group which can be split off as an anion, such as, for example, hydroxyl, a sulfate radical, a phosphate radical and Z stands for a direct bond or for a (x + 2) -valent organic Rest.

worin Z¹ eine direkte Bindung, einen Phenylenrest, insbesondere einen 1,4-Phenylenrest, oder einen Rest der Formel―(CH₂)y oder―(CH₂)_k―G―(CH₂)₁― darstellt, wobei y eine Zahl von 1 bis 6, k und I Zahlen von 1 bis 6 und G ―O―, ―S―, ―SO₂―, ―NH―, ―N(CH3)―, ―CO―, ―CHOH― oder Phenylen, insbesondere 1,4-Phenylen, bedeutet. Vorzugsweise sind k und I gleich und bedeuten vorzugsweise 1 oder 2, insbesondere 1.Z can be an aliphatic, aromatic or araliphatic radical, aliphatic and araliphatic radicals also keto groups -CO- or heteroatoms, such as ―0― or ―S―, or heteroatom groups, such as -SO-, -SO ₂ -, -NH-, -N (CH ₃ ) - may contain. In accordance with the preferred meaning of x = O, a divalent radical is preferred for Z, so that a bifunctional alkylation component is preferred as the polyfunctional alkylation component D. Particularly preferred bifunctional alkylating agents correspond to formula XII

wherein Z ^{1 is} a direct bond, a phenylene radical, in particular a 1,4-phenylene radical, or a radical of the formula― (CH ₂ ) y or― (CH ₂ ) _k ―G― (CH ₂ ) ₁ -, where y is a Number from 1 to 6, k and I numbers from 1 to 6 and G ―O―, ―S―, ―SO ₂ -, ―NH―, ―N (CH3) -, ―CO―, ―CHOH― or phenylene, especially 1,4-phenylene. K and I are preferably the same and are preferably 1 or 2, in particular 1.

Examples of preferred bifunctional alkylating agents of the formula XII are: epichlorohydrin (= chloromethyloxirane), epibromohydrin, 1,3-dichloro-propan-2-ol, 2,2'-dichlorodiethyl ether, 2,2'-dichlorodiethylamine, 2,2 ' -Dichlorodiethyl sulfide, 2,2'-dichlorodiethyl sulfoxide, 2,2'-dichlorodiethyl sulfone, 2,2'-bis (sulfato) ethyl ether, 2,2'-bis (phenyl sulfonyloxy) ethyl ether, 2 , 2'-bis (p-tolylsulfonyloxy) ethyl ether, diepoxy-butane, di-epoxy-2-methylbutane, bis-glycidylamine (= bis- (2,3-epoxypropyl) amine), 1,2- or 1,4-bis (epoxyethyl) benzene, 1,2- or 1,4-bis (2,3-epoxypropyl) benzene, 1,2- or 1,4-bis (chloromethyl) - benzene.

The polyamine component E can consist of a component E 'or E2 or of the two components E' and E ² .

In the formula VII of the polyamine component E ', s is preferably the number 2. In this case, preferred suitable representatives of the polyamine component E' of the formula VII are commercially available polyethyleneimines with a molecular weight between 2000 and 27000, preferably between 2000 and 20,000, particularly preferred between 2000 and 5000. Such polyethyleneimines are commercially available. They are made by polymerizing ethyleneimine and contain about 50 to 600 ethyleneimine units and usually primary, secondary and tertiary nitrogen atoms in a number ratio of about 1: 2: 1. The different nitrogen atoms are statistically distributed in the molecule. They are preferably used directly in the form of their commercially available aqueous solutions in the process for the preparation of the crosslinked copolymers.

mit Dicarbonsäuren der Formel XIV

im Molverhältnis 1: (0.5 bis 1) dar. u bedeutet vorzugsweise 2 oder 3 und w vorzugsweise 1, 2 oder 3.In the polyamine component E ^{2 of} the formula VIII, the alkylene radical representing R ²² can be delayed or preferably straight-chain. A phenylene radical representing R ²² is preferably a 1,4- or 1,2-phenylene radical. The compounds of formula VIII are reaction products of amines of formula XIII

with dicarboxylic acids of the formula XIV

in a molar ratio of 1: (0.5 to 1). u is preferably 2 or 3 and w is preferably 1, 2 or 3.

• H₂N―CH₂―CH₂―NH―CH₂―CH₂―NH₂
• H2_N―CH₂―CH₂―CH₂―NH―CH₂―CH₂―CH₂―NH₂,
• H₂N―CH₂―CH₂―NH―CH₂―CH₂―NH―CH₂―CH₂―CH₂―NH₂.
• H₂N―CH₂―CH₂―NH―CH₂―CH₂―NH―CH₂―CH₂―NH―CH₂―CH₂―NH₂.

Preferred amines of the formula XIII are, for example:

• H ₂ N ― CH ₂ ―CH ₂ ―NH ― CH ₂ ―CH ₂ ―NH ₂
• H2 _N ―CH ₂ ―CH ₂ ―CH ₂ ―NH ― CH ₂ ―CH ₂ ―CH ₂ ―NH ₂ ,
• H ₂ N ― CH ₂ ―CH ₂ ―NH ― CH ₂ ―CH ₂ ―NH ― CH ₂ ―CH ₂ ―CH ₂ ―NH ₂ .
• H ₂ N ― CH ₂ ―CH ₂ ―NH ― CH ₂ ―CH ₂ ―NH ― CH ₂ ―CH ₂ ―NH ― CH ₂ ―CH ₂ ―NH ₂ .

Suitable dicarboxylic acids of formula XIV are e.g. Oxalic acid, malonic acid, succinic acid, glutaric acid, adipic acid, pimelic acid, suberic acid, azelaic acid, sebacic acid, phthalic acid and isophthalic acid.

In the copolymer according to the invention the molar ratio A: B: C is preferably = 1: (0.02 to 2.5): 0. Crosslinked copolymers according to the invention are preferred in which the molar ratio B ': D: E = 1: (0.002 to 1) :( 0.05 to 5), preferably 1: (0.01 to 1) :( 0.1 to 4.5).

The starting components required for the preparation of the copolymers according to the invention are known or can be prepared by processes which are known for the respective class of substances.

The water-soluble copolymers according to the invention are prepared by copolymerizing the diallyl component A, the amide component B and the (meth) acrylic ester component C in a suitable solvent. Suitable solvents are water and water-miscible solvents such as e.g. lower alcohols, e.g. Methanol, ethanol, n-propanol, i-propanol, N-butanol, tert-butanol, glycols, such as e.g. Ethylene glycol, propylene glycol, di- and polyglycols such as e.g. Diethylene glycol, triethylene glycol, glycol ethers such as e.g. Diethylene glycol mono methyl ether, diethylene glycol mono ethyl ether, ethylene glycol mono methyl ether, ethylene glycol mono ethyl ether, ethylene glycol mono n-propyl ether, ethylene glycol mono n-butyl ether, Ethylene glycol di-methyl ether, ethylene glycol di-ethyl ether, ketones, such as Acetone or methyl ethyl ketone.

The copolymerization can also be carried out in a mixture of different solvents, preferably in a solvent mixture which contains small amounts of water. If e.g. the diallylammonium component A is used in the form of an aqueous solution, no further addition of water is normally necessary.

Before the start of the copolymerization, it is advisable to adjust the pH from 3 to 8.5. An acid, preferably an organic acid, in particular acetic acid, is generally used for this pH adjustment.

The copolymerization is carried out at temperatures from 40 to 100 ° C, preferably 60 to 90 ° C, very particularly preferably at temperatures from 65 to 85 ° C, and in a conventional manner, e.g. by adding suitable initiators. Suitable initiators are radical-forming substances, e.g. Benzoyl peroxide, tert-butyl hydroperoxide, cumene peroxide, methyl ethyl ketone peroxide, lauryl peroxide, tert. Butyl perbenzoate, ditert.Butyl perphthalate, azodiisobutyronitrile, 2,2'-azobis (2,4-dimethylvaleronitrile), 2-phenyl-azo-2,4-dimethyl-4-methoxyvaleronitrile, 2-cyano-2-propyl-azoformamide , Azodiisobutyramide, dimethyl, diethyl or di-n-butyl azobis methyl valerate, tert-butyl perneodecanoate, di-isononanoyl peroxide, tert-amyl perpivalate, di-2-ethylhexyl peroxydicarbonate, di- lauroyl peroxide, di-isotridecyl peroxydicarbonate, tert-butyl peroxy-isopropyl percarbonate. 2,2'-Azobis- (2-amidinopropane) dihydrochloride is preferably used as the initiator. Based on the amount of monomers of components A + B + C, 0.01 to 2% by weight, preferably 0.1 to 1% by weight, of initiator is used. It is expedient to carry out the copolymerization in the absence of oxygen. This can be done in a manner known per se by purging or passing an inert gas, e.g. Nitrogen. Components A, B, C, which can each consist of one or more individual components, are used in amounts such that the molar ratio A: B: C = 1: (0.002 to 4.5) :( O to 0.5) , preferably 1: (0.02 to 2.5): O.

The copolymerization is complete after about 30 minutes to about 4 hours, in many cases after 30 minutes to 2 hours. After the copolymerization has ended, an approximately 15 to 55% by weight solution is normally present.

To carry out the crosslinking reaction, the solution obtained in the copolymerization is reacted in the presence of water with a polyfunctional alkylation component D and preferably additionally with a polyamine component E. The polyamine component E can consist of a polyamine component E 'or E2 or a mixture of these components. If a polyamine component E is used in the crosslinking, it is added to the aqueous solution of the copolymer to be crosslinked before the polyfunctional alkylation component D. Based on 1 mol of the basic component B 'polymerized in the uncrosslinked copolymer, the molar ratio B': D: E in the crosslinking reaction is 1: (0.002 to 2) :( 0 to 5), preferably 1: (0.002 to 1) :( 0 , 5 to 5), particularly preferably 1: (0.01 to 1) :( 0.1 to 4.5). The crosslinking is carried out at temperatures from 30 to 90 ° C, preferably from 40 to 60 ° C, and is carried out after a few minutes, e.g. 5 to 20 minutes, preferably 5 to 10 minutes, by adding a mineral acid such as e.g. Hydrochloric acid, sulfuric acid, phosphoric acid or nitric acid terminated. A pH of 4 to 7 is set by adding the mineral acid.

The solutions of the crosslinked copolymer obtained in the preparation have an active substance content of approximately 25 to 55% by weight and can be used directly in this form, but preferably after dilution to an active substance content of approximately 25 to 35% by weight, as textile auxiliaries .

The solutions of the crosslinked copolymers according to the invention obtained in the preparation can be dissolved in water either real or at least killoidally. They are outstandingly suitable as textile auxiliaries, in particular for improving the authenticity of dyeings and printing reactive dyes on cellulose materials.

The aftertreatment of reactive dyeings and prints according to the invention is normally carried out in a liquor ratio of 1: 5 to 1: 3, preferably 1:10 to 1:20. A liquor is used which contains 0.5 to 6 g, preferably 1 to 3 g, of the copolymer according to the invention per liter. In special cases, the liquor ratio and auxiliary concentration can of course be varied beyond the normal limits indicated. The desired improvements in authenticity are basically achieved when the copolymer in the form of the approx. 25 to 55% by weight solution obtained in the production in an amount of 0.5 to 10%, preferably 1 to 8%, in particular 2 to 6 % of the product weight is applied. The aftertreatment is expediently carried out at temperatures from room temperature to 100 ° C., preferably up to 60 ° C., particularly preferably at room temperature. Then you only need to rinse once. There is a significant improvement in the fastness properties, in particular the wet fastness and rub fastness properties.

The copolymer according to the invention is also suitable for improving the authenticity of dyeings and prints with substantive and vat dyes. It is used in the same way as in the authenticity improvement of dyeings and prints with reactive dyes. In particular, it can also be used as an authenticity-improving aid for simultaneous quasi single-bath sizing and dyeing of cellulose materials with vat dyes. The copolymer in the form of the approx. 25 to 55% strength by weight solution obtained in the preparation is generally added to the size dye liquors in amounts of 20 to 80 g / l, preferably 30 to 60 g / l. A higher addition is possible, but is usually not necessary. Less than the specified additional quantities may also be sufficient in individual cases, e.g. if very light shades are colored or if there are not quite as high demands on the improvement of authenticity. The quasi single-bath size dyeing process using the copolymer according to the invention is carried out according to the size or size dyeing processes known per se and in the units used for this purpose. The fiber material to be processed is passed through the existing troughs of the unit in order, then dried and fed to the fiber supply of the further processing machine. More or less long air passages are normally switched on between the impregnation troughs of the finishing dyeing unit, the length of which is dimensioned in a known manner so that the dyeing time required for the dye used is achieved. The drying of the yarn impregnated in the impregnation troughs is carried out by supplying heat, generally by means of contact heat over drying rollers, and generally leads to the dyeing process being completed and the dye being completely fixed on the substrate. When carrying out the quasi single-bath sizing process using the copolymer according to the invention, it is particularly advantageous if, instead of the 3 water troughs common in most units, a fourth water trough is additionally switched on. The impregnating troughs are loaded with the sizing dye liquor in a conventional manner, the concentration of the sizing agent in the liquor being based on the amount of the size application required for the further processing process and on the fiber quality. For a given liquor intake, which is normally between 100 and 200%, the dye concentration depends on the desired depth of color. As a rule, the liquors contain 30 to 80 g per liter of sizing agent and 10 to 50 g per liter of the dye. It is advisable here to select the dye concentration in the first impregnation trough somewhat higher than in the following ones and to set the concentration of the sizing agent in the last troughs higher than in the previous ones. When using 4 drinking troughs, it is advantageous to work in the 4th drinking trough without the addition of colorants. The concentration of the copolymer according to the invention is expediently kept somewhat lower in the baths which have higher dye concentrations and a somewhat higher concentration of auxiliaries is used in baths which have lower dye concentrations. The auxiliary concentrations in the first bath are preferably set between 0 and 20 g / l, those in the last bath in the range from 20 to 60 g / l.

All commonly used products can be considered as sizing agents, e.g. Starch and starch derivatives, sizing agents based on carboxymethyl cellulose, vinyl homo- or copolymers, acrylate copolymers or water-soluble polyesters. The agents which are particularly suitable for cellulose materials are preferably used, in particular those based on starch and starch derivatives, carboxymethyl cellulose. Starch and starch derivatives are particularly preferred as sizing agents.

Vat dyes which can be found in the "Color Index", third edition, volume 3, pages 3727-3837 come into consideration as dyes for the finishing dyeing process.

The vat dye is added to the size dyeing liquor in its reduced and thus water-soluble form. Concentrated aqueous solutions of the vat dyes made water-soluble by reduction are referred to below as stock vats, in particular in the exemplary embodiments. The manufacture of these stumps is known. It is carried out by heating aqueous dispersions of the vat dyes, which are inherently water-insoluble, with reducing agents, sodium dithionite ("hydrosulfite") being generally used.

In addition to the coupled or reduced dyes, the known sizing agents and the authenticity-improving aids to be used according to the invention, the sizing dye liquors can also contain other auxiliaries and additives as are known from customary dyeing processes. In particular, it is advantageous to add known dyeing accelerators and wetting and dispersing agents to the liquors in the usual concentrations. If necessary, reducing agents can also be added, which prevent reoxidation of the linked dyes.

The use of the copolymers according to the invention achieves a very considerable improvement in the wet fastness of the size dyeings. In addition, there is also an improved sizing of the yarn through better film formation of the sizing agent. Finally, an increased weaving efficiency can also be determined.

In addition, the copolymer according to the invention can also be used as a textile aid for improving the authenticity of dyeings and prints, in particular with reactive dyes and substantive dyes, on textiles made from cellulose fibers and their mixtures with synthetic fibers, which are then subjected to finishing or finishing. Such equipment or refinement e.g. an easy-care finish, a wash-and-wear finish, a low-wrinkle and low-shrink finish or a permanent fixation of calender effects. The implementation of the high refinement is known. The textile materials are treated with reactant resins, e.g. treated on the basis of N-methylol-dihydroxy-ethylene urea or of N-dimethylol-dihydroxy-ethylene urea, which crosslink in the presence of acid donors with the hydroxyl groups of the cellulose fibers. The textile material is treated with a high-quality liquor that contains the reactant resin in amounts of approx. 30 to 250 g / liter, catalyst, e.g. Contains zinc chloride or magnesium chloride and optionally other auxiliaries, additives, plasticizers, fillers and / or water repellents. The copolymer according to the invention in the form of the 25 to 55% by weight solution obtained in the preparation in amounts of e.g. 10 to 70 g / liter, preferably 20 to 50 g / liter, added. The material treated with the refining liquor is then dried. The reactant resin is then condensed on the goods at elevated temperature. The condensation is usually carried out for 3 s to 4 minutes at 150 ° C. or 60 to 30 seconds at 170 to 185 ° C. A post-washing process is usually not carried out. The fastness properties, in particular the wet fastness properties, are considerably improved in some cases by using the copolymers according to the invention as part of a high-level finishing.

In the following examples, temperatures are given in degrees Celsius. Unless otherwise specified, parts are parts by weight and percentages are percentages by weight.

example 1

122.5 g of ethanol, 150 g of a 60% strength aqueous solution of dimethyldiallylammonium chloride, 10 g of dimethylaminopropylmethacrylamide and 3 are placed in a 700 ml 4-necked flask equipped with an anchor stirrer, thermometer, reflux condenser, gas inlet tube and dropping funnel , 5 g of acetic acid. The solution is then heated to an internal temperature of 70 to 75 ° C. while nitrogen is passed through and 0.2 g of the initiator 2,2'-azobis- (2-amidinopropane) dihydrochloride is added at 60 to 65 ° C. The copolymerization begins at 76 to 77 ° C. The mixture is then stirred for a further 2 h at an internal temperature of 76 to 77 ° C. 22.2 g of a commercially available polyethyleneimine with an average molecular weight of 3000 to 5000 in the form of a 50% strength aqueous solution and then 0.536 g of epichlorohydrin are added and stirring is continued at 78 ° C. for 15 minutes. The crosslinking is then ended by adding 13.8 g of sulfuric acid (diluted 1: 1 with water) and adjusting to a pH of 7.

The active ingredient content is then adjusted to 30% with water.

Yield: 330 g.

• K-Wert vor der Copolymerisation: 16,3 x 10³,
• K-Wert nach der Copolymerisation: 24,8 x 10³,
• K-Wert nach der Vernetzung: 34,4 x 10³.

The course of the copolymerization and crosslinking can be seen from the measured K values of the solution.

• K value before copolymerization: 16.3 x 10 ³ ,
• K value after copolymerization: 24.8 x 10 ³ ,
• K value after crosslinking: 34.4 x 10 ³ .

Example 2

122.5 g of ethanol, 158.3 g of a 60% strength aqueous solution of diallyl-dimethyl-ammonium chloride and 5 g of dimethylaminopropyl methacrylamide are placed in a 700 ml 4-necked flask equipped with an anchor stirrer, thermometer, reflux condenser, gas inlet tube and Heated to 70 to 75 ° C while introducing nitrogen. At 60 ° C 0.2 g tert. Butyl perbenzoate is added, and the copolymerization begins at 70 ° C., which is completed by stirring at 70 to 75 ° C. Then 3 ml of a 1.6% ethanolic epichlorohydrin solution are added, stirring is continued for 5 min at 70 ° C. and, after cooling with water, adjusted to a 30% solution.

Example 3

122.5 g of methyl glycol, 83.3 g of a 60% strength aqueous solution of dimethyl-diallyl-ammonium chloride, 50 g of dimethylaminoethyl-methacrylic acid ester are placed in a 700 ml 4-necked flask equipped with an anchor stirrer, thermometer, reflux condenser and gas inlet tube submitted and adjusted to a pH of 8.5 with 3.8 g of glacial acetic acid. Then nitrogen is introduced into a Internal temperature of 80 ° C heated and at 60 ° C internal temperature 0.2 g of 2,2'-azobis (2-amidinopropane) dihydrochloride and copolymerized in the temperature range of 76 to 80 ° C. The mixture is then stirred for 2 hours. 22 g of a condensation product of 1 mol of adipic acid and 1 mol of diethylene triamine and then 2.052 g of epichlorohydrin in the form of a 10% strength ethanolic solution are then added. After stirring for 10 to 20 minutes at 70 ° C., the crosslinking of the copolymers is complete. Now the solution is adjusted to a pH of 7.0 by adding 1.5 g of H ₂ SO ₁ (diluted 1: 1 with water).

• K-Wert vor der Copolymerisation: 15,7 x 10³,
• K-Wert nach der Copolymerisation und Vernetzung: 78,8 x 10³.

The yield is 698.7 g of a 15% solution.

• K value before copolymerization: 15.7 x 10 ³ ,
• K value after copolymerization and crosslinking: 78.8 x 10 ³ .

Example 4

122.5 g of i-propanol, 83.3 g of a 60% solution of dimethyldiallylammonium chloride and 50 g of dimethylaminopropylmethacrylamide are placed in a 700 ml 4-necked flask equipped with an anchor stirrer, thermometer, reflux condenser and gas inlet tube , adjusted to a pH of 8.5 with 12.9 g of glacial acetic acid and heated to an internal temperature of 75 to 80 ° C. while introducing nitrogen. 0.2 g of 2,2'-azobis- (2-amidinopropane) dihydrochloride are added at 50 °. The copolymerization begins between 72 and 74 ° C and is ended by stirring at 80 ° C.

22 g of the condensation product of 1 mol of adipic acid and 1 mol of diethylenetriamine are then added in the form of an aqueous solution. Then 0.821 g of epichlorohydrin are added and crosslinked at 50 ° C. for 10 minutes.

The pH is then adjusted to 7 by adding 9.8 g of H ₂ SO ₄ (1: 1 diluted with water).

• K-Wert der Lösung vor der Copolymerisation: 17,3 x 10',
• K-Wert der Lösung nach der Copolymerisation: 30,6 x 10³,
• K-Wert der Lösung nach der Vernetzung: 42 x 10³.

The yield is 315 g in the form of a 30% solution.

• K value of the solution before the copolymerization: 17.3 x 10 ',
• K value of the solution after the copolymerization: 30.6 x 10 ³ ,
• K value of the solution after crosslinking: 42 x 10 ³ .

Example 5

122.5 g of ethylene glycol, 150 g of a 60% strength aqueous solution of dimethyl-diallyl-ammonium chloride, 10 g of dimethylaminopropyl methacrylamide are placed in a 700 ml 4-necked flask equipped with an anchor stirrer, thermometer, reflux condenser and gas inlet tube, with 3. 5 g of glacial acetic acid are adjusted to a pH of 8.5 and heated to 75 to 80 ° C. while introducing nitrogen. 0.1 g of 2,2'-azobis- (2-amidinopropane) dihydrochloride are added at 55 °. The copolymerization begins in the temperature range from 70 to 74 ° C. and is completed by reheating at 80 ° C. for 2 h. Now 22.2 g of polyethyleneimine (50% aqueous solution) and 30 ml of water and 0.536 g of epichlorohydrin in alcoholic solution are added. The mixture is crosslinked at 70 ° C. for 20 minutes and then the reaction is interrupted by adding H ₂ SO ₄ (diluted 1: 1 with water) and adjusting to a pH of 7.0.

• An einer 1%igen Lösung wurden folgende Werte gefunden:
• K-Wert vor der Copolymerisation: 16,3 x 10³,
• K-Wert nach der Copolymerisation: 24,8 x 10³,
• K-Wert nach der Vernetzung: 34,4 x 10³.

The yield is 344 g of a 30% copolymer solution. The reaction is monitored by measuring the K value:

• The following values were found on a 1% solution:
• K value before copolymerization: 16.3 x 10 ³ ,
• K value after copolymerization: 24.8 x 10 ³ ,
• K value after crosslinking: 34.4 x 10 ³ .

Application example 1

A boiled cotton jersey is dyed in a liquor containing 3% C.I. Reactive Blue 89, 3% C.I. Reactive Black 5, 1 g / 1 of a commercially available water softener based on polyphosphate, 50 g / I Glauber's salt and 20 g / I soda lime. included. The dyeing is carried out for 1 h at a dyeing temperature of 60 ° C., then the sample is neutralized cold with acetic acid and rinsed with hot water for 10 min.

After a boiling soap, a 20-minute treatment at room temperature is carried out in a solution which contains 5% of a product according to the invention according to Example 1 or 5, calculated on the dry weight of the goods. Then it is rinsed cold only once. The authenticity values given in column 3 below for the bleeding of undyed cotton accompanying fabric are obtained. For comparison, column 2 shows the values for the fastness properties which can only be obtained with boiling soap without subsequent treatment with a textile auxiliary. For comparison, column 4 shows the values for the fastness properties which are obtained with 5% of a commercially available textile auxiliary on the basis of a peralkylated polyamine.

Example of use 2

• 65 g/I ®Arkofix NG konz. (handelsübliches Hockveredelungsmittel der Firma HOECHST AG, Frankfurt/Main 80, auf der Basis von Dimethylol-dihydroxy-ethylenharnstoff. Arkofix ist ein eingetragenes Warenzeichen der HOECHST AG).
• 10 g/I Polyethylen-Dispersion
• 60 g/I Zirkoniumoxychlorid-Paraffin-Emulsion
• 1 ml/l Essigsäure, 60%ig,
• 20 g/I MgCl₂ . 6 H₂0
• 40 g/I Produkt gemäß Beispiel 5.

500 m of a viscose lining material are first washed on a jigger with 2 g / l detergent based on a reaction product of 1 mol 4-nonylphenol and 10 mol ethylene oxide at 60 ° C for 30 min, rinsed and then with 4% CI Direct Red 23 Colored for 60 min at 60 to 90 ° C with the addition of 10% sodium sulfate. After rinsing with cold water and drying, the fabric is padded on a padder as follows:

• 65 g / I ® Arkofix NG conc. (Commercial high-quality finishing agent from HOECHST AG, Frankfurt / Main 80, based on dimethylol-dihydroxy-ethylene urea. Arkofix is a registered trademark of HOECHST AG).
• 10 g / l polyethylene dispersion
• 60 g / l zirconium oxychloride paraffin emulsion
• 1 ml / l acetic acid, 60%,
• 20 g / l MgCl ₂ . 6 H ₂ 0
• 40 g / l product according to example 5.

• Handelspräparat 1 auf der Basis von peralkyliertem Polyamin
• Handelspräparat 2 auf der Basis eines Aminhydrochlorid/Dicyandiamid/Formaldehyd-Kondensationsproduktes.

The fabric was dried at 110 ° C and then condensed at 150 ° C for 4 min. The goods treated and finished in this way, when determining the wash fastness for mechanical washing at 60 ° C. in accordance with DIN 54010, have a fastness rating of 5. For comparison, the fastness scores are given in the table below, which are obtained without textile auxiliaries and with equal amounts of commercially available textile auxiliaries :

• Commercial preparation 1 based on peralkylated polyamine
• Commercial preparation 2 based on an amine hydrochloride / dicyandiamide / formaldehyde condensation product.

Example of use 3

• 65 g/I ®Arkofix NDS konz. (handelsübliches Hockveredelungsmittel der Firma HOECHST AG, Frankfurt/Main 80, auf der Basis von modifiziertem N-Methylol-dihydroxy-ethylenharnstoff)
• 20 g/l MgCl₂ 6H₂O
• 30 g/1 erfindungsgemäßes Produkt gemäß Beispiel 10
• 20 g/I Weichmacher Hoe-T-3492-1 (handelsüblicher Weichmacher der Firma HOECHST AG, Frankfurt/Main 80, auf der Basis eines Fettsäurekondensationsproduktes) enthält.

A 5% dyeing is made on cotton jersey with CI Reaktiv Blue 89 and through Rinsing, boiling soaping and drying finished. The dry dyeing is padded with the following equipment fleet, the

• 65 g / I ® Arkofix NDS conc. (commercially available high-quality finishing agent from HOECHST AG, Frankfurt / Main 80, based on modified N-methylol-dihydroxy-ethylene urea)
• 20 g / l MgCl ₂ 6H ₂ O
• 30 g / 1 product according to the invention according to Example 10
• Contains 20 g / l plasticizer Hoe-T-3492-1 (commercial plasticizer from HOECHST AG, Frankfurt / Main 80, based on a fatty acid condensation product).

It is then dried at 110 ° C. and condensed at 150 ° C. for 4 minutes. By adding the copolymer according to the invention according to Example 5, the water fastness (heavy duty) according to DIN 54006 and the fastness properties against acidic and alkaline sweat according to DIN 54020 are increased by 1 grade compared to a product without aftertreatment, as can be seen from the following table.

It should also be noted that the wet light fastnesses are not reduced compared to the use of commercially available dicyandiamide / formaldehyde condensation products or peralkylated polyamines.

Example of use 4

• 65 g/l ®Arkofix NG konz. (handelsüblicher Katalysator der Firma HOECHST AG, Frankfurt/Main 80, auf der Basis von Metallsalzen)
• 15 g/I MgCl₂ 6 H₂0
• 20 g/I ^®Leomin NI (handelsüblicher Weichmacher der Firma HOECHST AG, Frankfurt/Main 80, auf der Basis eines Fettsäurekondensationsproduktes. Leomin ist ein eingetragenes warenzeichen der HOECHST AG.)
• 30 g/I des Produkts gemäß Beispiel 3 enthält. Anschließend wird bei 110°C getrocknet und 4 min bei 150°C kondensiert. Durch den Einsatz des erfindungsgemaßen Copolymerisats werden die Wasser- und Schweißechtheiten deutlich verbessert, ohne daß die Naßlichtechtheiten verschlechtert werden.

A 4% dyeing of CI Reactive Orange 82 on cotton fabric is completed by rinsing, boiling soaping and drying and padded in dry condition with a finishing liquor that

• 65 g / l ®Arkofix NG conc. (commercial catalyst from HOECHST AG, Frankfurt / Main 80, based on metal salts)
• 15 g / l MgCl ₂ 6 H ₂ 0
• 20 g / I ^® Leomin NI (commercial plasticizer from HOECHST AG, Frankfurt / Main 80, based on a fatty acid condensation product. Leomin is a registered trademark of HOECHST AG.)
• Contains 30 g / l of the product according to Example 3. It is then dried at 110 ° C. and condensed at 150 ° C. for 4 minutes. By using the copolymer according to the invention, the water and sweat fastness are significantly improved without the wet light fastness being impaired.

Application example 5

• 65 g/I @Arkofix NDS konz. (handelsübliches Hochveredelungsmittel der Firma HOECHST AG, Frankfurt/Main 80, auf der Basis von modifiziertem N-Methylol-dihydroxy-ethylenharnstoff)
• 20 g/I Katalysator 3282 (handelsüblicher Katalysator der Firma HOECHST AG, Frankfurt/Main 80, auf der Basis von Metallsalzen)
• 20 g/I des Weichmachers Hoe-T-3492-1 (handelsüblicher Weichmacher der Firma HOECHST AG, Frankfurt/Main 80, auf der Basis eines Fettsäurekondensationsproduktes)
  enthält. Anschließend wird bei 110°C getrocknet und 4 min bei 150°C kondensiert. Zum Vergleich wird eine Ware hergestellt, die noch zusätzlich 30 g/I der erfindungsgemaßen Copolymerlösung nach Beispiel 5 enthält.

A 4% dyeing of CI Reactive Orange 82 on cotton fabric is completed by rinsing, and boiling soaping and drying, and padded in a dry state with a finishing liquor that

• 65 g / I @Arkofix NDS conc. (commercial high-quality finishing agent from HOECHST AG, Frankfurt / Main 80, based on modified N-methylol-dihydroxy-ethylene urea)
• 20 g / l catalyst 3282 (commercially available catalyst from HOECHST AG, Frankfurt / Main 80, based on metal salts)
• 20 g / l of the plasticizer Hoe-T-3492-1 (commercial plasticizer from HOECHST AG, Frankfurt / Main 80, based on a fatty acid condensation product)
  contains. It is then dried at 110 ° C. and condensed at 150 ° C. for 4 minutes. For comparison, a product is produced which additionally contains 30 g / l of the copolymer solution according to the invention according to Example 5.

Compared to the goods without the copolymer according to the invention of Example 5, the fastness to heavy water and the fastness to perspiration are improved acid and alkaline by one grade without the wet light fastness being impaired.

Application example

• 65 g/I ®Arkofix NG konz. (handelsübliches Hochveredelungsmittel der Firma HOECHST AG, Frankfurt/Main 80, auf der Basis von Dimethylol-dihydroxy-ethylenharnstoff)
• 15 g/I MgCl₂· 6 H₂O
• 20 g/I ®Leomin NI (handelsüblicher Weichmacher der Firma HOECHST AG, Frankfurt/Main 80, auf der Basis eines Fettsäurekondensationsproduktes)
  enthält. Anschließend wird bei 110°C getrocknet und 4 min bei 150°C kondensiert. Zum Vergleich wird noch eine Ware hergestellt, die zusätzlich 30 g/l der erfindungsgemaßen Copolymerisat nach Beispiel 4 enthält.

A 4% dyeing of CI Reactive Blue 89 on cotton fabric is completed by rinsing, boiling soaping and drying and padded in the dry state with a finishing liquor which

• 65 g / I ® Arkofix NG conc. (commercially available high-quality finishing agent from HOECHST AG, Frankfurt / Main 80, based on dimethylol-dihydroxy-ethylene urea)
• 15 g / l MgCl ₂ .6 H ₂ O
• 20 g / I ®Leomin NI (commercial plasticizer from HOECHST AG, Frankfurt / Main 80, based on a fatty acid condensation product)
  contains. It is then dried at 110 ° C. and condensed at 150 ° C. for 4 minutes. For comparison, another product is produced which additionally contains 30 g / l of the copolymer according to the invention from Example 4.

By using the copolymer solution according to the invention according to Example 4, the fastness to heavy water and the fastness to perspiration are increased by one grade without the wet light fastness being impaired.

Application example 7

• 2% C.I. Reactive Red 123
• 2% C.I. Reactive Red 124
• 1 g/l eines handelsüblichen Wasserenthärtungsmittels auf der Basis Polyphosphat 25 g/I glaubersalz enthält. Man färbt 10 min bei 40°C, setzt weitere 25 g/I Glaubersalz und nach weiteren 30 min 20 g/I Soda zu. Nach einer weiteren Stunde ist die Färbung beendet.

Boiled and bleached cotton yarn is dyed in a fleet that

• 2% CI Reactive Red 123
• 2% CI Reactive Red 124
• 1 g / l of a commercially available water softener based on polyphosphate contains 25 g / I Glauber's salt. It is dyed at 40 ° C. for 10 minutes, a further 25 g / l of Glauber's salt is added, and 20 g / l of soda are added after a further 30 minutes. The coloring is finished after another hour.

After dyeing, the mixture is neutralized, as usual, cold with acetic acid, rinsed and treated with 5% of the product (based on the dry weight) of Example 3 for 20 min at pH 6.

• ^*Als handelsübliches Hilfsmittel wurde eines auf der Basis von peralkyliertem Polyamin verwendet.

A dyeing is obtained with significantly improved fastness properties, which are determined by the staining of undyed cotton accompanying fabric:

• ^* One based on peralkylated polyamine was used as a commercial aid.

In the same way, improvements are obtained if the dyeings are produced using the PAD-Steam, PAD-Jigg or cold dwell process.

Claims (11)

1. Process for preparing a copolymer characterised in that

a) a diallylammonium component A of the formula I

and

b) an amide component B consisting of a basic component B¹ of the formula II

and optionally an amide component B² of the formula III

and/or an N-vinylacylamide component B³ of the formula IV

and/or an ammonium component B⁴ of the formula V

and

c) a (meth)acrylic ester component C of the formula VI

are copolymerized in a molar ratio A:B:C = 1 :(0.002 to 4.5):(0 to 0.5) in water or in a solvent miscible with water at temperatures from 40 to 100°C and are subsequently reacted in a aqueous medium with

d) a polyfunctional alkylation component D and

e) a polyamine component E consisting of a polyamine component E¹ of the formula VII

and/or a polyamine component E² of the formula VIII

in a molar ratio B¹:D:E of 1:(0.002 to 2):(0 to 5), at temperatures between 30 and 80°C,

R¹, _R ², _R ⁵, R⁶ and R²¹ being (C₁―C₁₀)-alkyl,

_R ³, R⁴, R⁷, R⁸, R¹¹, R¹², R¹⁸, R¹⁹ and R²⁰ being hydrogen or methyl,

R⁹, R¹⁰ and R¹³ being hydrogen or (C₁―C₈)-alkyl,

R'⁴, R'⁵, R¹⁶ and R¹⁷ being (C₁―C₈)-alkyl or

R¹³ and R¹⁴ together being ―(CH₂)₃―, -(CH₂)₄- or ―(CH₂)_s―,

R²² being an alkylene radical having 1 to 8 C atoms or phenylene,

R²³ being hydrogen or the radical ―CO―R²²―COOH,

X being -NH- or ―O―

Y^⊖, Z^⊖ being a monovalent anion or a portion of a polyvalent anion equivalent to a monovalent anion,

T being ⁅(CH₂)_s―NH ⁆_vH

m and q being one of the numbers 2, 3, 4, 5, 6, 7, 8, 9 or 10,

n, p, r and w being one of the numbers 0, 1, 2 or 3,

s and u being one of the numbers 2, 3, 4 or 5,

v being the number 0 or a number of such magnitude that, taking into account t, the polyamine component E¹ has a molecular weight of 1000 to 30,000 and

t being a number of such magnitude that, taking account of v, the molecular weight of the polyamine component E¹ of the formula VII is between 1000 and 30,000.

₂. Process according to Claim ₁, characterized in that R¹, R², R⁵, R⁶, R¹⁴, R¹⁵, R¹⁶ and/or R¹⁷ denote (C₁-C₄)-alkyl and/or that R³ and/or R⁴ denote hydrogen and/or R⁹, R¹⁰ and/or R¹³ denote hydrogen or (C₁―C₄)-alkyl.

3. Process according to Claim 1 and/or 2, characterized in that n and/or p and/or r denote 0.

4. Process according to one or more of Claims 1 to 3, characterized in that the molar ratio A:B:C is 1:(0.02 to 2.5):0.

5. Copolymer according to one or more of Claims 1 to4, characterized in that the molar ratio B¹:D:E is 1:(0.002to 1):(0.05to 5).

6. Use of the copolymer prepared according to one or more of Claims 1 to 5 as a textile auxiliary.

7. Use of the copolymer prepared according to one or more of Claims 1 to 5 as a textile auxiliary for improving the fastness of dyeings and prints obtained with reactive dyestuffs.

8. Use of the copolymer prepared according to one or more of Claims 1 to 5 as a textile auxiliary for improving the fastness of dyeings and prints obtained with substantive dyestuffs and/or vat dyestuffs.

9. Use of the copolymer prepared according to one or more of Claims 1 to 5 as a textile auxiliary for improving fastness in the quasi one-bath sizing and dyeing of cellulose materials with vat dyestuffs.

10. Use of the copolymer prepared according to one or more of Claims 1 to 5 as a textile auxiliary for improving the fastness of dyeings and prints on cellulose materials which are subjected to finishing or permanent finishing.